DE1569470A1 - Processing aids for rubber compounds - Google Patents

Description

D R-I NG. G. Rl E BL I N G

PATENT ADVOCATE

156947O

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899 Lindau (Bodensee) Rennerle 10 Posthcfa 36S

October 27, 1965

TECHNICALPROCESSING, INC., 106, RAILROADAVENUE, PATERSON, NEW JERSEY / USA

Processing aids for rubber compounds

IXSXXZIXXXSXXIIIIXIXXISXSXIJIXIISIKX

The invention relates to new additives that are used in processing of rubber compounds are helpful.

During the grinding of rubber stocks, it is general

Practice making the rubber compounds detackifying

d. H. Add release agents, such as low molecular weight polyethylene

9098 33/1275

Ferntchralber: Talking about bank account: Pottery checking account

4374 pat rlabllng Il by agreement Bayer. SUatibank Lindau (B) No. 1M2 ^: Munich 295 25

and soaps to help separate the rubber from the grinder to facilitate. These release agents have to be added in relatively large amounts in order to achieve the desired effect perform. In such compositions, the release agents change the physical properties to a great extent of the rubber masses and in many cases influence them their adhesive properties.

The new compositions according to the invention help in the separation the rubber compounds from the mill without changing the physical properties of such compounds and · without the adhesive properties to disturb the rubber compounds in the subsequent processing stages. In addition, these new masses help even when bonding rubber laminates tightly during curing. The compositions of the invention also improve the surface appearance of molded or extruded rubber articles, improve the dispersion of fillers in the rubber compound and provide low Mooney viscosities without changing the hardness of the rubber compounds.

According to the invention, homogeneous binders are therefore provided which contain approximately 10-14% of an oleate salt of bivalent Metals from the group zinc, aluminum, calcium, electricity

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tium and barium, about 5-8% of a potassium soap, made essentially with saturated fatty acids of about 12-18 Carbon atoms in the chains, approximately 14-17% essentially saturated fatty acids with about 12-18 carbon atoms in the chains, about 4-20% of a compound from the group of polyethylene glycol alkyl ethers, polyethylene glycol alkyl phenol ethers and polyethylene glycol monoesters of fatty acids, the polyethylene glycol component being the compound Molecular weight between about 100 and 400 and the alkyl part the compound has from about 12 to 20 carbon atoms, about 5-10% alkyl glycols with water and oil solubility and 1-4 methyl or methylene groups, not directly with the hydroxyl group and polyglycols of this compound connected, about 3 - 5% alkylols from the group of branched and straight-chain compounds with about 11-18 Carbon atoms in the chain and about 40 - 50% paraffins from the group of petrolatum, mineral oil and paraffin waxes.

A preferred composition according to the invention contains approximately 10-14 % zinc oleate, approximately 5-8% of a potassium soap, essentially made with saturated fatty acids with a chain length of approximately 16-18 carbon atoms, approximately

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14-17% saturated fatty acids with a chain length of approximately 16-18 carbon atoms, about 4-20% tetraethylene glycol-honylphenol ether, about 5-10% tripropylene glycol, about 3-5% of a straight chain alkylol with about 16-18 Carbon atoms in the chain and about 40-50% petroleum jelly. The percentages of the masses above and in the following description are based on total weight.

The homogeneous binders according to the invention are prepared by heating the above ingredients together to a clear melt is obtained. The metal oleate and the potash soaps of the inventive masses can in situ during of heating in a known manner. A general process for the preparation of the fiction according to en Masses is done as below:

An oxide, hydroxide or carbonate of a divalent metal is mixed with oleic acid in approximately stoichiometric amounts or reacted in a slight excess of about 0.25-2% oleic acid to the corresponding oleate salts. The reaction temperature is between about 90 and 130 C. and preferably 95 - 105 C. This temperature range also applies

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on the other stages of making this mixture. That Metal and the oleic acid are heated together until one clear melt is obtained and all of the water of reaction has evaporated. After the oleate is formed, the alkylol, paraffin compound and fatty acid become the Reaction mass was added and the entire mixture was stirred. A potassium oxide, hydroxide or carbonate is then added and stir the mixture until a clear mass has been formed. The polyethylene glycol compound and the Alkylpolyglykolver bond are then added to the reaction mass and heated until a clear melt is obtained.

The above method can be explained by referring to the following preferred procedure for the production of compositions according to the invention:

10.5 g oleic acid and 1.3 g zinc oxide are heated together to about 100 g until a clear melt is obtained _; and substantially all of the water of reaction has evaporated. Then 3.9 g of technical grade cetyl alcohol, 42.8 g of Vaseline US.P and 18.5 g of hydrogenated tallow fatty acids are added. The temperature is brought to about 90-95 ° C. and 1.7 g potassium hydroxide 45% strength is added with mixing. The tempera- "

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door is then brought to about 100 C. and mixing continued until the mass is clear. Then 15.4 g of tetraethylene glycol nonylphenol ether are added and 7, 7 g of tripropylene glycol admixed. Heat is only applied to one at this stage to obtain clear melt. The compound is then ready for filling into suitable containers.

The compositions of the invention are added to the rubber during mixing. In ordinary blending raw rubber is first masticated to make it more pliable and then mixed with other additives, such as pigments d. H. Carbon black, fillers, e.g. B. zinc, magnesium, lead or calcium oxide, vulcanizing agents z. B. Sulfur, etc. The compositions according to the invention can be mixed with these additives in order to bring about a uniform distribution. In general approximately 0.25-0.75% of the compositions according to the invention, based on the total weight of the rubber component used.

The compositions according to the invention can be used for any type of rubber be added, be it natural, synthetic or reclaimed rubber.

909833/1275

The following masses made by the above procedure explain the new compositions according to the invention.

Mass A.-'.-. ■■■■ - .. ·

11.0 grams of zinc oleate

5.2 g potassium soap made from hydrogenated sebum soaps 14.0 g hydrogenated tallow fat soaps, 15.4 g tetraethylene glycol nonylphen oil ether 7.7 g tripropylene glycol

3.9 g of cetyl alcohol, technical 42.8 g of Vaseline U. S. P.

. ■ mass. B.

10.7 g of magnesium oleate

5.5 g potassium stearate 14.0 g stearic acid, technical 15.4 g of hexaethylene glycol dodecylphenol ether 7, 7 g of tripropylene glycol 3.9 g cetyl alcohol, technical grade

909833 / T27S

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Dimensions

12.0 grams of calcium oleate

5.2 g potassium stearate

14.0 g stearic acid technical

17.7 g of hexaethylene glycol dodecylphenol ether

5.4 grams of propylene glycol

3.0 g of 5-ethyl-2-nonanol

42.7 g paraffin wax, refined

Mass D

13.3 g barium oleate 7, 7 g potassium stearate 17.0 g of stearic acid, technically 12.0 g of polyglycol 400 monolaurate

8.0 g tripropylene glycol

4, og cetyl alcohol, technical 5.0 g mineral oil 100/100 33.0 g of Vaseline U. S. P.

Mass E

14.0 g zinc oleate

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8, O g potassium stearate
17.0 g stearic acid, technical

4, 3 g tetraethylene glycol nonylphenoläther 8.6 g 2 _a 4-Dibydroxy-2-methyl pentane

4.4 g of cetyl alcohol, technical grade
43.7 g of Vaseline USP

Each of the above compositions of the present invention is made into rubber given and tested for its effectiveness in separating the rubber mass during grinding. The results of this Tests are listed in Examples 1-5 below. the The rubber base of each of the examples was as follows:

H art ρ ac kungs basic dimensions

100.00 parts 38 % acrylonitrile rubber

20.00 "Durez resin 12687 (thermosetting phenolic resin)

5.00 "zinc oxide

1. 50 "stearic acid.

170.00 "mean thermal soot 30.00 "silicate filler, particle size 0.025 microns

12. 50 "dibutyl phthalate

15.00 "coumarone-indene resin

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1.00 part diethylene glycol

1.00 "sulfur

1. 75 "benzothiazyl disulfide

Example I.

358. 25 parts of hard pack matrix, as above 1.00 "mass A

Example II

358. 25 parts of hard pack base mass, as above 1.00 "mass B

Example III

358. 25 parts of hard pack basic mass, as above 1.00 "mass C

Example IV

358. 25 parts of hard packing base compound, as above 1.00 "compound C

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Example V

358 »25 parts hard pack basic dimensions, as above 1.00 "mass E.

The compositions of Examples 1-5 all give good grinder separation. When these resin packing bases with no additive used so was the separation from the mill not satisfactory.

Each of the compositions A to E were tested for binding properties by curing the compositions e.g. B. I to V at 160 ° C (320 ° F) for 10 minutes by placing two strips of each surface-to-surface mass in a mold. The compositions of Examples I and II show a perfect tight bond and no delamination prior to breakage. The mass of Example I breaks an average of 32.66 kg (72 lbs) and that of Example II averages 33.11 kg (73 lbs). The masses of example ΙΙΪ show almost perfect bonding. The necessary for separating force was almost the one that is necessary ¹ ujn ground breaking. The mass begins to delaminate at an average of 28.58 kg (63 lbs) and breaks when you see your face ^ 32.66 kg (72 lbs). the

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156P470

Masses of Example IV and V did not give a perfect bond; however, considerable force was still required - about 75% of that required to break the masses - to drive the strips to separate. Both of these masses begin delaminating at an average of approximately 25.40 kg (56 lbs); both Masses can be severed before they break.

The following examples explain the use of the fiction, according to Masses for a wide variety of rubbers.

Example VI

50.0 parts smoked leaves (natural rubber)

94.0 "total tire regenerated rubber (natural and SBR regenerated rubber)

5. 0 "aromatic oil

1.0 "stearic acid

3.0 "zinc oxide

1.0 "phenyl-d-naphthylamine

2.5 "sulfur

1.0 "2,2 '- benzothiazyl disulfide

0.1 "zinc dimethyl dithiocarbamate.

100.0 "" FT Russ

40.0 "MPC Russ 909833/1275

1.5 ⁿ ground A

The separation of the rubber compound with the compound A from the Mill was good - while the mill separation of the rubber mass without preparation A was poor.

The rubber compound with compound A had a Mooney plasticity / 1 + 4 './ 100 ° C (212 ° F) of 102.0 and a Mooney plasticity without mass A of 117.0.

The mass A rubber mass was about 20 minutes cured at 143.3 C (290 F) and showed a Shore hardness of 86 and had the same hardness as when it was hardened without Compound A at the same time and temperature.

Example VII

100. 0 Parts Butyl rubber 1.0 Il Stearic acid 5. 0 Il Zinc oxide 1.0 Il Phenyl-d -maphthylamine 1.0 Il Paraffin wax 2.0 Il sulfur 0.5 Il 2-mercaptobenzothiazole 1.0 Il Tetramethylthiuram disulfide 909833/1275

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1.0 parts tellurium diethyl dithiocarbamate

5. 0 "aromatic oil

10.0 "MPC Russ

70. 0! ' FEF Russ

1.0 "mass B

The separation of the rubber composition of Example VII with composition B from the mill was good, while the mill separation of the same rubber compound without compound B was bad.

The above rubber composition contained composition B and then had one Mooney plasticity / 1 + 4 '/ 100 ° C (212 ° F) of 74.0 and a Mooney plasticity of 76.0 with no mass B.

The mass according to Example VH had a Shore hardness of 15 minutes Cure time at 160 ° C (320 F) of 77 and the same hardness when cured in the same time and temperature without mass B.

The invention is only intended to be illustrated and not limited by the examples given.

Claims

XSJe = SXx = XXKX = SX

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Claims (4)

156P47Q Claims (Jlj release agent for rubber, characterized by approximately 10 - 14% of an oleate salt of bivalent metals from the group of zinc, magnesium, calcium, strontium and barium approximately 5 - 8% of a potassium soap, produced essentially with saturated fatty acids of approximately 12; - 18 carbon atoms in the chain, about 14-17% of essentially saturated fatty acids with about 12-18 carbon atoms in the chain, about 4-20% of a compound from the group consisting of polyethylene glycol alkyl ethers, polyethylene glycol alkyl phenol ethers and polyethylene glycol monoesters of fatty acids _? the polyethylene glycol portion of the compound has a molecular weight between about 100 and 400 and the alkyl portion of the compound has about 12-20 carbon atoms, about 5-10% alkyl glycols have both water and oil solubility and 1-4 groups selected from methyl and methylene radicals, the nicjit i - "■ ■■ .""■ -. '. directly to the Uydxostylg & ippe. and the polyglycols of the · Verhiridting are bound, about 3 - 5% alkylols from the group of; branched and straight-chain compounds with about 11-18 carbon atoms in the chain and about 40-59% paraffins from the group of petrolatum, mineral oil and paraffin wax. 2. Release agent according to claim 1, characterized by about 10 to 14% zinc oleate, about 5-8% of a potash soap, made essentially from saturated fatty acids with a chain length of about 16-18 carbon atoms, about 14-17% saturated fatty acids with a chain length of about 16-18 carbon atoms, about 4-20% tetraethylene glycol nonylphenol ether, about 5-10% tripropylene glycol, about 3-5% of a straight chain alkylol with about 16-18 carbon atoms in the chain and about 40-50% petroleum jelly. 3. Rubber compound characterized by a rubber base, carbon black, fillers and a relatively small amount of the Release agent according to claim 1, 4. Rubber compound characterized by a rubber base, a thermosetting resin, carbon black, fillers and a relatively small amount of the release agent according to claim 2. 909833/1275